CN113842933B - 一种有机化二氧化硅负载PMoW多酸光催化材料及其制备方法和应用 - Google Patents
一种有机化二氧化硅负载PMoW多酸光催化材料及其制备方法和应用 Download PDFInfo
- Publication number
- CN113842933B CN113842933B CN202111271968.4A CN202111271968A CN113842933B CN 113842933 B CN113842933 B CN 113842933B CN 202111271968 A CN202111271968 A CN 202111271968A CN 113842933 B CN113842933 B CN 113842933B
- Authority
- CN
- China
- Prior art keywords
- pmow
- polyacid
- silicon dioxide
- silica
- microspheres
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 56
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 39
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000004005 microsphere Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 15
- 239000002351 wastewater Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000010842 industrial wastewater Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000003053 toxin Substances 0.000 claims description 9
- 231100000765 toxin Toxicity 0.000 claims description 9
- 108700012359 toxins Proteins 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 5
- 230000008520 organization Effects 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000003242 anti bacterial agent Substances 0.000 claims description 4
- 229940088710 antibiotic agent Drugs 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 239000011964 heteropoly acid Substances 0.000 description 11
- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 241000195493 Cryptophyta Species 0.000 description 7
- 230000000593 degrading effect Effects 0.000 description 7
- 229960003276 erythromycin Drugs 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 201000007270 liver cancer Diseases 0.000 description 2
- 208000014018 liver neoplasm Diseases 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种有机化二氧化硅负载PMoW多酸光催化材料,其于由PMoW多酸和有机化二氧化硅微球组成,PMoW多酸负载在有机化二氧化硅微球表面,所述PMoW多酸为H3PMonW(12‑n)O40·xH2O,其中1<n<12,有机化二氧化硅微球和PMoW多酸的质量比为1:0.1~1:2,所述有机化二氧化硅负载PMoW多酸光催化材料的孔隙率为62%。
Description
技术领域
本发明属于工业废水处理光催化材料领域,具体涉及一种有机化二氧化硅负载PMoW多酸光催化材料及其制备方法和应用。
背景技术
随着经济发展,大量难降解工业废水被肆意排入环境,由此引起的水质污染已成为我国乃至全球环境污染的一个重要问题。医药工业、养殖业有机废水多以难降解抗生素为主,此类废水具有极高的亲水性和生物蓄积性,对人类的健康有着极大的危害。化肥农药的过度施用也导致水中藻类过度繁殖,其产生得藻毒素也使得水中的有害物进一步攀升,在肝癌高发区流行病的调查表明,饮用藻茵类毒素污染的水是肝癌的主要原因。综上,难降解有机废水无害化处理刻不容缓。难降解有机废水的处理工艺主要包括生物方法、物理方法和化学方法。由于微生物对有机废水降解有其天然的劣势,所以生物方法并不能有效降解水中的有机污染物。物理方法去除水中的有机物主要利用多孔物质对水中有机物的吸附,该方法有效工作面积小,且不能降解有机污染物,易形成二次污染物。因此利用化学方法对有机废水进行无害化降解具有广阔的应用前景。
目前对于难降解工业废水的处理主要依赖于催化氧化降解,其中光催化具有独特的优势。光催化降解难降解有机物,克服了传统热催化降解对能源得依赖。目前,光催化应用的主要问题是催化材料成本较高,这主要是由于目前用于废水处理的多依赖于贵金属。而贵金属的价格昂贵、比表面积小,不利于产业化应用,因此寻找廉价的载体、提高金属分散度、改善催化剂电子传输性能是光催化技术发展的关键问题。
非贵金属杂多酸盐结构相对稳定,有能够快速可逆的转移电子的能力,成为光催化剂的重要研究方向之一。纳米二氧化硅是一种轻质的多孔纳米材料,是一种无毒、无味的无机非金属材料,呈絮状和网状的准颗粒结构,为球形,具有比表面积大,密度小和分散性能好等特性。多酸催化剂表现出了极佳的废水净化能力,Mo-POM最近已被用作光催化剂用于催化降解有机废水。但目前采用传统浸渍法合成的POM/SiO2复合材料存在的主要问题是杂多酸与二氧化硅结合得不牢固,易从二氧化硅上脱落下来,使杂多酸在反应过程中流失掉。
发明内容
针对现有技术的不足,本发明公开了一种有机化二氧化硅负载PMoW多酸光催化材料及其制备方法和应用,本发明是通过以下技术方案实现的:
一种有机化二氧化硅负载PMoW多酸光催化材料,其由PMoW多酸和有机化二氧化硅微球组成,PMoW多酸负载在有机化二氧化硅微球表面,所述PMoW多酸为H3PMonW(12-n)O40·xH2O,其中1<n<12,有机化二氧化硅微球和PMoW多酸的质量比为1:0.1~1:2。
所述有机化二氧化硅负载PMoW多酸光催化材料的孔隙率为62%。
一种有机化二氧化硅负载PMoW多酸光催化材料的制备方法,包括以下步骤:
步骤1:制备二氧化硅微球:将0.3g四乙氧基硅烷和1ml十六烷基三甲基溴化铵溶于乙醇水溶液中,滴加氨水调节至pH=8,50℃下搅拌48小时,将混合物冷却至室温,离心分离浆液,用蒸馏水洗涤3次后冷冻干燥,置于石英坩埚中,773 K下煅烧6小时制得二氧化硅微球;
步骤2:二氧化硅微球有机化:取步骤1制得的二氧化硅微球超声分散于N,N-二甲基甲酰胺溶液中,加入硅烷偶联剂KH-560,加入1mol/L氢氧化钠溶液调节pH=9,室温下搅拌2小时,将所得浆液转入聚四氟乙烯反应釜中,80℃条件下反应12小时,离心分离浆液,80℃蒸馏水洗涤三次,冷冻干燥,得有机化二氧化硅微球;
步骤3:制备有机化二氧化硅负载PMoW多酸光催化材料:取步骤2制得的有机化二氧化硅微球 2g,超声分散在去62.5ml去离子水中;将2.15 g磷酸氢二钠溶解于溶液中12.5mL去离子水;8.71 g钼酸钠溶解于25ml去离子水中;将有机化二氧化硅水溶液、磷酸氢二钠水溶液、钼酸钠水溶液三种溶液混合,90℃条件下搅拌30分钟后,向混合液中加入11.88 g钨酸钠溶液,添加浓H2SO4调整pH=1.5,所得浆液继续在90℃条件下搅拌8小时,冷冻干燥,所得固体用60℃乙醇溶液洗涤3次,300℃条件下加热4小时,所得产物即有机化二氧化硅负载PMoW多酸复合材料。
步骤1中的煅烧的条件如下:纯度为99.999% 的N2气氛,气体流量100~200 mL/min,以5℃/min速率升温至700℃,煅烧时间为6 h。
步骤2中每0.1克二氧化硅微球加入10ml N,N-二甲基甲酰胺;加入与二氧化硅微球等质量的硅烷偶联剂KH-560。
步骤3中钨酸钠溶液浓度为0.1mol/L。
一种有机化二氧化硅负载PMoW多酸光催化材料的应用,用于处理废水,所述废水为有机毒素含量较高(2000mg/L)的工业废水或含大量(2000mg/L)抗生素的养殖废水。优选地,所述废水为有机毒素含量较高的工业废水或含大量抗生素的养殖废水。
本发明将PMoW杂多酸负载在有机化的二氧化硅球核上,提高了其分散度,增强了PMoW杂多酸活性的同时还增加了复合材料的比表面积、孔隙率,有效地实现高效降解工业废水污染物的特性。本发明的有益效果如下:
1、本发明的有机化二氧化硅负载PMoW多酸光催化材料,其主要成分PMoW多酸有着独特的结构,使其更易吸附有机污染物;PMoW多酸中的金属原子大多处于其最高价态,电负性强,高富氧表面赋予其强氧化能力,PMoW多酸在温和条件下也表现出快速可逆的氧化还原能力;杂多酸所特有的金属含氧簇结构使得PMoW多酸具有类似半导体(TiO2)的特性,在光照情况下表面可产生大量•OH自由基,具有强氧化性,可氧化降解工业废水中的有机物。
2、本发明通过在有机化的二氧化硅微球表面负载PMoW多酸,制得有机化二氧化硅负载PMoW多酸光催化材料。对二氧化硅表面进行有机化,利用介孔二氧化硅表面得硅羟基将有机官能团直接引入到材料中,利用有机官能团和C多酸形成更稳定得结合,提高二氧化硅负载PMoW多酸在反应过程中的使用寿命,克服了杂多酸与二氧化硅结合得不牢固,易从二氧化硅上脱落的缺点。PMoW杂多酸负载在有机化的二氧化硅球核上,提高了其分散度,增强了PMoW杂多酸活性的同时还增加了复合材料的比表面积、孔隙率,有效地实现高效降解工业废水污染物的特性。本发明利用对二氧化硅表面进行有机化,再负载PMoW多酸获得的光催化材料呈现多孔海胆状结构,孔隙率高,比表面积大,膜通量大,具有高效降解有机污染物特性。
附图说明
图1为实施例2制得的有机化二氧化硅负载PMoW多酸光催化材料的XRD图;
图2为实施例2制得的有机化二氧化硅微球的TEM图;
图3为实施例2有机化二氧化硅负载PMoW多酸光催化材料的SEM图;
图4为实施例2制得的有机化二氧化硅负载PMoW多酸光催化材料用于降解红霉素和藻毒素的降解率图。
具体实施方式
下面结合附图与实施例对本发明做进一步详细说明。
实施例1
一种二氧化硅负载PMoW多酸光催化材料的制备方法,包括以下步骤:
步骤1)制备二氧化硅微球:将四乙氧基硅烷(CTAB,0.3g)和十六烷基三甲基溴化铵(TEOS,1ml)溶于乙醇的水溶液(乙醇103.8mL、蒸馏水82.8mL))中,滴加氨水调节至pH=8,50℃调节下搅拌48小时,将混合物冷却至室温,离心分离浆液,用蒸馏水洗涤3次;所获产物冷冻干燥后,置于石英坩埚中,773 K下煅烧6小时制得二氧化硅微球。
步骤2)二氧化硅微球有机化:取步骤1)制得的二氧化硅微球超声分散于N,N-二甲基甲酰胺溶液中,加入一定量的硅烷偶联剂KH-560,加入1mol/L氢氧化钠溶液调节pH=9,室温下搅拌2小时,将所得浆液转入聚四氟乙烯反应釜中,80℃条件下反应12小时。离心分离浆液,80℃蒸馏水洗涤三次,冷冻干燥,所得产物即有机化二氧化硅微球C-SiO2。
本实施例制得的有机化二氧化硅微球C-SiO2的TEM图如图2所示,由图可知,制得的有机化二氧化硅微球C-SiO2呈表面粗糙的圆形,直径约200nm。
实施例2
一种有机化二氧化硅负载PMoW多酸光催化材料的制备方法,具体步骤如下:
步骤1)制备二氧化硅微球:将四乙氧基硅烷(CTAB,0.3g)和十六烷基三甲基溴化铵(TEOS,1ml)溶于乙醇的水溶液(乙醇103.8mL、蒸馏水82.8mL))中,滴加氨水调节至pH=8,50℃调节下搅拌48小时,将混合物冷却至室温,离心分离浆液,用蒸馏水洗涤3次;所获产物冷冻干燥后,置于石英坩埚中,773 K下煅烧6小时制得二氧化硅微球。
步骤2)二氧化硅微球有机化:取步骤1)制得的二氧化硅微球超声分散于N,N-二甲基甲酰胺溶液中,加入一定量的硅烷偶联剂KH-560,加入1mol/L氢氧化钠溶液调节pH=9,室温下搅拌2小时,将所得浆液转入聚四氟乙烯反应釜中,80℃条件下反应12小时。离心分离浆液,80℃蒸馏水洗涤三次,冷冻干燥,所得产物即有机化二氧化硅微球C-SiO2。
步骤3)制备有机化二氧化硅负载PMoW多酸光催化材料:取步骤2)制得的有机化二氧化硅微球C-SiO2 2g,超声分散在去62.5ml去离子水中,将磷酸氢二钠(2.15 g,6 mmol)溶解于溶液中12.5 mL去离子水,同时添加钼酸钠(8.71 g,36 mmol)溶解于25ml去离子水中,将上述三种溶液混合,90℃条件下搅拌30分钟后。向混合液中加入钨酸钠溶液(11.88g),逐滴添加浓H2SO4以调整pH=1.5,所得浆液继续在90℃条件下搅拌8小时。冷冻干燥,所得固体用60℃乙醇溶液洗涤3次,300℃条件下加热4小时,所得产物即二氧化硅负载PMoW多酸复合材料。
本实施例制得的有机化二氧化硅负载PMoW多酸光催化材料的XRD图如图1所示,PMoW多酸的结晶程度良好,图中未见与二氧化硅相关物种的峰,PMoW多酸负载在二氧化硅微球得表面。
本实施例制得的有机化二氧化硅负载PMoW多酸复合材料的SEM图如图3所示,由图可知,制得的材料是多孔海胆状结构纤维状的多孔网络结构,直径在500nm范围内。
实例3
将实施例2制得的二氧化硅负载PMoW多酸复合材料作为光催化剂应用于光催化污水处理装置中(实验室模拟的污水),以常见的难降解的红霉素和高毒性的藻毒素为降解对象,考察其对实际工业废水中典型高毒性难降解污染物的降解效能。如图4所示为实施例2制得的二氧化硅负载PMoW多酸光催化材料用于降解红霉素和藻毒素的降解率图,由图4可知,实施例2制得的有机化二氧化硅负载PMoW多酸光催化材料50min时对红霉素得去除率达到了90%以上,60min时对藻毒素的去除率达到了90%以上,实施例2制得的有机化二氧化硅负载PMoW多酸复合材料光催化降解红霉素和藻毒素效果明显。
Claims (5)
1.一种有机化二氧化硅负载PMoW多酸光催化材料的制备方法,包括以下步骤:
步骤1:制备二氧化硅微球:将0.3g四乙氧基硅烷和1ml十六烷基三甲基溴化铵溶于乙醇水溶液中,滴加氨水调节至pH=8,50℃下搅拌48小时,将混合物冷却至室温,离心分离浆液,用蒸馏水洗涤3次后冷冻干燥,置于石英坩埚中,773 K下煅烧6小时制得二氧化硅微球;
步骤2:二氧化硅微球有机化:取步骤1制得的二氧化硅微球超声分散于N,N-二甲基甲酰胺溶液中,加入硅烷偶联剂KH-560,加入1mol/L氢氧化钠溶液调节pH=9,室温下搅拌2小时,将所得浆液转入聚四氟乙烯反应釜中,80℃条件下反应12小时,离心分离浆液,80℃蒸馏水洗涤三次,冷冻干燥,得有机化二氧化硅微球;
步骤3:制备有机化二氧化硅负载PMoW多酸光催化材料:取步骤2制得的有机化二氧化硅微球 2g,超声分散在去62.5ml去离子水中;将2.15 g磷酸氢二钠溶解于溶液中12.5 mL去离子水;8.71 g钼酸钠溶解于25ml去离子水中;将有机化二氧化硅水溶液、磷酸氢二钠水溶液、钼酸钠水溶液三种溶液混合,90℃条件下搅拌30分钟后,向混合液中加入11.88 g钨酸钠溶液,添加浓H2SO4调整pH=1.5,所得浆液继续在90℃条件下搅拌8小时,冷冻干燥,所得固体用60℃乙醇溶液洗涤3次,300℃条件下加热4小时,所得产物即有机化二氧化硅负载PMoW多酸复合材料,所述有机化二氧化硅负载PMoW多酸光催化材料由PMoW多酸和有机化二氧化硅微球组成,PMoW多酸负载在有机化二氧化硅微球表面,所述PMoW多酸为H3PMonW(12-n)O40·xH2O,其中1<n<12,有机化二氧化硅微球和PMoW多酸的质量比为1:0 .1-1:2,材料的孔隙率为62%。
2.根据权利要求1所述的有机化二氧化硅负载PMoW多酸光催化材料的制备方法,其特征在于步骤1中的煅烧的条件如下:纯度为99.999% 的N2气氛,气体流量100~200 mL/min,以5℃/min速率升温至700℃,煅烧时间为6 h。
3.根据权利要求1所述的有机化二氧化硅负载PMoW多酸光催化材料的制备方法,其特征在于步骤2中每0.1克二氧化硅微球加入10ml N,N-二甲基甲酰胺;加入与二氧化硅微球等质量的硅烷偶联剂KH-560。
4.根据权利要求1所述的有机化二氧化硅负载PMoW多酸光催化材料的制备方法,其特征在于步骤3中钨酸钠溶液浓度为0.1mol/L。
5.如权利要求1所述的有机化二氧化硅负载PMoW多酸光催化材料制备方法制得的材料的应用,用于处理废水,所述废水为含有机毒素的工业废水或含抗生素的养殖废水。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111271968.4A CN113842933B (zh) | 2021-10-29 | 2021-10-29 | 一种有机化二氧化硅负载PMoW多酸光催化材料及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111271968.4A CN113842933B (zh) | 2021-10-29 | 2021-10-29 | 一种有机化二氧化硅负载PMoW多酸光催化材料及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113842933A CN113842933A (zh) | 2021-12-28 |
CN113842933B true CN113842933B (zh) | 2023-05-09 |
Family
ID=78983555
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111271968.4A Active CN113842933B (zh) | 2021-10-29 | 2021-10-29 | 一种有机化二氧化硅负载PMoW多酸光催化材料及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113842933B (zh) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108160115A (zh) * | 2018-01-12 | 2018-06-15 | 浙江工业大学 | 一种磷钼钨杂多酸催化剂的可控制备方法 |
-
2021
- 2021-10-29 CN CN202111271968.4A patent/CN113842933B/zh active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108160115A (zh) * | 2018-01-12 | 2018-06-15 | 浙江工业大学 | 一种磷钼钨杂多酸催化剂的可控制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN113842933A (zh) | 2021-12-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107754785B (zh) | 一种用于低温催化氧化甲醛的石墨烯-氧化锰复合催化剂及其制备方法 | |
CN107376851A (zh) | 一种部分硫化金属有机框架复合材料的制备方法及其应用 | |
CN102974375A (zh) | 一种异质结构多功能复合材料及其制备方法 | |
CN111744503A (zh) | 一种Z型异质结MoS2/Bi2WO6复合光催化剂及其制备方法和应用 | |
CN110354845A (zh) | 一种碳纳米点修饰的钨酸铋光催化剂及其制备方法和应用 | |
CN113786839A (zh) | 一种复合微球结构ZnO/CuO/GO异质结光催化剂及其制备方法和应用 | |
CN113842933B (zh) | 一种有机化二氧化硅负载PMoW多酸光催化材料及其制备方法和应用 | |
CN113398914A (zh) | 一锅水热合成可见光催化剂的制备方法 | |
CN116637630B (zh) | 磺酸改性活性焦负载纳米金团簇双调控复合材料及其制备方法和应用 | |
CN111468100B (zh) | 一种原位生长的多酸铌/石墨烯光催化剂的制备方法及其在降解四环素中的应用 | |
CN113499773A (zh) | 一种纳米氧化锌负载钯纳米粒子的纳米酶及其制备方法和应用 | |
CN112774664A (zh) | 一种具有光热协同作用纳米TiO2@MnO2复合材料及其制备方法和应用 | |
CN109772380B (zh) | 氢化二氧化钛复合三维花球氯氧铋光催化剂及制备方法 | |
CN111686769A (zh) | 一种光催化剂及其制备方法和应用 | |
CN111229200A (zh) | 一种氧化铋改性Ti3+自掺杂TiO2异质结光催化剂的制备方法 | |
CN107262128B (zh) | 可见光响应型多孔氮化硼基复合光催化材料及制备方法 | |
CN111135839A (zh) | 一种氧化铁改性凹凸棒石/钼酸铋复合光催化剂及其制备方法和应用 | |
CN112657555B (zh) | 一种单分散Fe-O簇掺杂的Ni基金属有机骨架复合光催化剂及其制备方法与应用 | |
CN114377696B (zh) | 生物膜基BiOClxBr(1-x)/Au/MnO2复合材料及其制备方法和应用 | |
CN109046341A (zh) | 一种可见光响应的硅酸银/凹凸棒复合催化剂的制备方法 | |
CN1586202A (zh) | 一种复合型无机抗菌剂的制备方法 | |
CN112108166B (zh) | 一种超薄Bi4O5Br2/Bi2O2CO3可见光催化剂及其制备方法与应用 | |
CN111229279B (zh) | 一种氮化碳量子点负载多级孔反蛋白石结构CuO-SiO2的制备及其应用 | |
CN115739147A (zh) | 一种长余辉/红磷复合材料及其制备方法与其在孔雀石绿降解中应用 | |
CN109304224A (zh) | 长效水净化材料及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |